Synthesis and Characterization of Nanopore Mo<sup>VI</sup>-Imprinted Polymer and Its Application as Solid Phase for Extraction, Separation and Preconcentration of Molybdenum Ions from Water Samples

Ardestani, Fatemeh; Hosseini, Majid Haji; Taghizadeh, Majid; Pourjavid, Mohammad Reza; Rezaee, Mohammad

doi:10.5935/0103-5053.20160026

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Articles • J. Braz. Chem. Soc. 27 (7) • July 2016 • https://doi.org/10.5935/0103-5053.20160026 copy

Synthesis and Characterization of Nanopore Mo^VI-Imprinted Polymer and Its Application as Solid Phase for Extraction, Separation and Preconcentration of Molybdenum Ions from Water Samples

Authorship SCIMAGO INSTITUTIONS RANKINGS

The purpose of this study is to prepare a new ion imprinted polymer for Mo^VI with high selectivity. Ion-imprinted polymer (IIP) particles were synthesized by thermally copolymerization. For the synthesis of the ion imprinted polymer, the ion pair of (Mo^VI-thiocyanate) and NR₄⁺ was used. The ion pair was precipitated in an aqueous phase and then dissolved in acetonitrile as a porogen. The imprinted ion was removed using 10% (v/v) methanol in HCl (0.5 mol L^-1). The unleached and leached IIP particles were characterized by infrared spectroscopy, thermogravimetric analysis, surface area analysis, scanning electron microscopy and energy dispersive X-ray analysis. The use of the new Mo^VI-IIP in solid phase extraction revealed a maximum adsorption capacity of 3.77 mg Mo^VIper gram of Mo^VI-IIP in optimum conditions of extraction. The selectivity coefficients of the IIP for Mo in comparison with other metal ions were also evaluated. The proposed Mo-IIP was successfully applied for Mo^VI determination in different types of water samples.

Keywords:
ion imprinted polymer; molybdenum(VI); thermal copolymerization; solid phase extraction

ICP-AES^a a ICP-AES: inductively coupled plasma-atomic emission spectroscopy; condition
RF^b b RF: radiofrequency. generator power / kW	1.3
Frequency of RF^b b RF: radiofrequency. generator / MHz	40
Plasma gas flow rate / (L min^-1)	15.0
Auxiliary gas flow rate / (L min^-1)	1.0
Nebulizer pressure flow rate / (L min^-1)	0.8
Viewing high / mm	15
Sample flow rate / (mL min^-1)	1.5
Mo wavelength / nm	202.030

	BET^a a BET: Brunauer-Emmett-Teller; surface area /(m² g^-1)	Pore volume^b b by method BET; / (cm³ g^-1)	Pore diameter^c c by method BJH-Barrett-Joyner-Halenda; / nm
IIP -leached^d d IIP: ion imprinted polymer;	160.8 (48.94^e e reference 21; , 23.0^f)	0.26 (0.1349^e e reference 21; , 0.59^f f reference 24; )	1.83 (11.02^e e reference 21; , 1.5-10^f f reference 24; )
NIP^g g NIP: non-imprinted polymer.	72.1 (51.64^e e reference 21; )	0.07 (0.1359^e e reference 21; )	1.436 (10.53^e e reference 21; )
Unleached-IIP	29.4	0.04	1.434

Factor	Level
Factor	Low	Center	High
A: time / min	0.0	30.0	60.0
B: HCl / (mol L^-1)	0.3	1.65	3.0
C: NR₄⁺ (mol ratio)	0.0	35.0	70.0
D: SCN^– (mol ratio)	50.0	325.0	600.0

Number	time / min	HCl / (mol L^-1)	NR₄⁺(mol ratio)	SCN⁻(mol ratio)	Response
1	30	1.65	35	325	46.8
2	0	0.3	0	50	14.0
3	60	3	0	50	42.8
4	30	1.65	35	325	40.4
5	30	3	35	325	67.6
6	0	0.3	70	50	5.9
7	0	0.3	0	600	11.8
8	0	3	0	600	89.4
9	60	0.3	0	50	9.8
10	60	0.3	70	50	3.8
11	30	1.65	35	325	42.2
12	30	1.65	35	325	39.8
13	30	1.65	35	325	39.2
14	0	3	0	50	24.4
15	60	3	70	50	28.7
16	0	3	70	50	34.5
17	60	3	70	600	100.0
18	30	1.65	35	325	42.3
19	30	1.65	35	600	67.4
20	60	1.65	35	325	44.3
21	30	1.65	0	325	31.1
22	30	1.65	35	325	43.9
23	30	1.65	35	50	8.1
24	30	0.3	35	325	8.2
25	60	3	0	600	100.0
26	60	0.3	0	600	8.4
27	30	1.65	70	325	43.1
28	60	0.3	70	600	17.4
29	30	1.65	35	325	35.5
30	0	0.3	70	600	17.2
31	0	3	70	600	100.0
32	0	1.65	35	325	36.9

Term	Coefficient	SE coefficient^a a SE coefficient: standard error of coefficient;	p ^b b p: statistical parameter;
Constant	4.8037	5.96111	0.431
time / min	−0.0963	0.26582	0.722
HCl / (mol L^-1)	7.3069	6.98126	0.310
NR₄⁺ (mol ratio)	0.0822	0.22784	0.723
SCN⁻ (mol ratio)	0.0030	0.03330	0.929
time × time	0.0018	0.00405	0.654
HCl × HCl	−0.5746	2.00213	0.778
NR₄⁺ × NR₄⁺	−0.0015	0.00298	0.623
SCN⁻ × SCN⁻	−0.0000	0.00005	0.745
time × HCl	0.0504	0.03631	0.183
time × NR₄⁺	−0.0017	0.00140	0.233
time × SCN⁻	0.0000	0.00018	0.967
HCl × NR₄⁺	0.0082	0.03112	0.796
HCl × SCN⁻	0.0400	0.00396	0.000
NR₄⁺ × SCN⁻	0.0003	0.00015	0.085
S^c c S: standard deviation; = 5.882	R-sq^d d R-sq: regression-squared; = 97.6%	R-sq(adj)^e e R-sq(adj): regression-squared adjusted. = 95.6%

Source	DF^a a DF: Degrees of freedom;	Seq. SS^b b Seq. SS: sequential sum of squares;	Adj. SS^c c Adj. SS: adjusted sum of squares;	Adj. MS^d d Adj. MS: adjusted mean squares = Adj. SS / DF;	F^e e F: F-value is calculated with: Adj. MS for any parameter to Adj. MS of residual error;	p ^f f p: statistical parameter.
Regression	14	23673.1	23673.14	160.94	48.87	0.000
Linear	4	19854.9	63.74	15.94	0.46	0.764
Square	4	51.7	51.69	12.92	0.37	0.824
Interaction	6	3766.5	3766.53	627.76	18.14	0.000
Residual error	17	588.2	588.21	34.60
Lack-of-fit	10	507.3	507.34	50.73	4.39	0.031
Pure error	7	80.9	80.87	11.55
Total	31	25261.4

Source	DF^a a DF: Degrees of freedom;	Seq. SS^b b Seq. SS: sequential sum of squares;	Adj. SS^c c Adj. SS: adjusted sum of squares;	Adj. MS^d d Adj. MS: adjusted mean squares = Adj. SS / DF;	F^e e F: F-value is calculated with: Adj. MS for any parameter to Adj. MS of residual error;	p ^f f p: statistical parameter.
Regression	3	23338.2	23338.2	7779.41	235.96	0.000
Linear	2	19809.6	983.8	491.90	14.92	0.000
Interaction	1	3528.7	3528.7	3528.66	107.03	0.000
Residual error	28	923.1	923.1	32.97
Lack-of-fit	5	321.8	321.8	64.36	2.46	0.063
Pure error	23	601.3	601.3	26.14
Total	31	24261.4

Sorbent	K_d /(mL g^-1)
Sorbent	Mo^VI
IIP	48.90
NIP	2.32

Binary mixture of Mo/metal foreign ions	Concentration of ions / (mg L^-1)	Recovery of ion / %	K_d^a a Kd: Distribution coefficient; / (mL g^-1)	k^b b k: selectivity coefficients,
Cr^III Mo^VI	0.25 0.25	5.6 56.6	5.93 130.43	22
Pb^II Mo^VI	0.25 0.25	5.4 47.4	5.70 90.26	16
Cd^II Mo^VI	0.25 0.25	12.5 62.2	14.28 164.63	12
Mg^II Mo^VI	0.25 0.25	0.0 49.6	0.00 98.26	∞^c c very selectivity;
Zn^II Mo^VI	0.25 0.25	0.0 48.0	0.00 92.50	∞^c c very selectivity;
Co^II Mo^VI	0.34 0.25	32.6 48.9	48.47 95.65	2
Fe^III Mo^VI	2.58 0.25	8.9 57.5	9.80 135.25	14
Mn^II Mo^VI	0.25 0.25	8.5 55.9	9.29 126.72	14
U^VI Mo^VI	0.50 0.25	5.9 46.4	6.25 86.67	14
MoVI^d d without foreign ions.	0.25	33.6	48.90	−

Sample	Molybdenum concentration added / (µg L^-1)	Molybdenum concentration found / (µg L^-1)	Recovery / %
Anzali lake	0.0	not detected	−
Anzali lake	300.0	298.8 (± 3.9)^a a RSD: relative standard deviation.	99.6
Tap water	300.0	274.9 (± 4.3)^a a RSD: relative standard deviation.	91.6

Method	Relative standard deviation / %	Dynamic linear range / (µg L^-1)	Limit of detection / (µg L^-1)	Extraction time / min	Preconcentration factor	Reference
C-SPE^a a C-SPE: Colorimetric solid phase extraction; (sample volume: 1 mL)	3.3 (9.6)^c c RSD in mg L-1.	500-12000	200	5	−	27
SPE-ICP-AES^b b SPE-ICP-AES: solid phase extraction-inductively coupled plasma- atomic emission spectrometry; (sample volume: 50 mL, eluent: 10 mL HNO₃ 0.5 mol L^-1)	6.52 (0.5)^c c RSD in mg L-1.	4.3 (quantification limit)	1.3	20	5	28
Solid phase spectroscopy (sample volume: 50 mL)	1.7-2.6	50-2500	2	30	−	24
SPE-ICP-AES^b b SPE-ICP-AES: solid phase extraction-inductively coupled plasma- atomic emission spectrometry; (sample volume: 500 mL, eluent: 5mL HNO₃ 2 mol L^-1)	3	−	0.17	30	100	29
SPE-ICP-AES^b b SPE-ICP-AES: solid phase extraction-inductively coupled plasma- atomic emission spectrometry; (sample volume: 35 mL, eluent: 7 mL HCl 3 mol L^-1)	4.6 (0.5)^c c RSD in mg L-1.	10-1000	8.66	20	5	this work

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Synthesis and Characterization of Nanopore MoVI-Imprinted Polymer and Its Application as Solid Phase for Extraction, Separation and Preconcentration of Molybdenum Ions from Water Samples

Synthesis and Characterization of Nanopore Mo^VI-Imprinted Polymer and Its Application as Solid Phase for Extraction, Separation and Preconcentration of Molybdenum Ions from Water Samples